Process and paste for printing fabrics made of cellulose, such as textile fabrics, paper and the like, with chromium mordant dyestuffs



Patented Dec. 14, 1948 UNITED STATES 2,45a471... 1

PROCESS AND PASTE FOR PRINTING V RIOS MADE OF CELLULOSESUCHASTEX TILE FABRICS, RAPER- AND 'THE LIKE, WITH CHROMIUM. MORDANT DY-EST UFFS Ernst Tschair, Basel; Switzerland; assignorwt'oi Durand & Huguenirr A. G.," BaseL'switzerland;

No-Di'a-wing.- Application March-'15,,1945;Serial;

No. 583,007. In Switzerland February 17,1944

Section 1, Public Law 690," August 8;"1'946 Patent expires February 17;..11964 I 1 As known, the chromium mordantv d'yestufi had formerly always to be fixed bya prolonged steam, In order to obtain a'complete formation of the chromium lake, a steaming of at least45 ing.

minutes was required."'After the knowledge of readily fixable dyestuffs, such as vat dyestuffs, ester salts of leuco vat dyestuffsfand naphthol dyestuffs, the necessity of a long steaming has been felt as a drawback. by the consumers. Con.-

sequentl'y the application of "chromium mordant dyestuffs has retrograded considerably.

However. the abovem'entioned drawback. was

overcome to some extent, inasmuch as the formationof the'l'ake could be accelerated a. good deal by the addition to the printing pastes of car'- boxylic acid amides, such as urea,v formamide or" acetamide (see Melliand Textilber'ichte1933,.'page.

412 and 1934', page 362: Ueber einige Fortschritte in der Anwendung der Chromfarbstofie by Ciuvon Niederhausern, and French Patent No. 8650677.

It is further known, that the chromium mordant dyestuffs can be fixed on cellulose fibres by a steamingof 8 minuteswith th'e ass-istanceof so dium chromate in presence of a reducing agent (see Recipes, Durand- &' Huguenin- S. A.-,, part II second edition, pages 39 et seq.).

These different processes: already represented a considerable technical improvement" compared with former long steaming processes. They facilitated considerably the practical application of the chrome mordant dyestuffs. Thus a great number of chromium mordant dyestuffs could now well be fixed on cellulose fibres by a steaming of5-8" minutes in a Mather-Flatt ager. But, when working according to the above 'm'entionedproc esses with a short steamingduration; it'was impossible to obtain a yield as good as'that" obtainedby the application of the "formerprocesses with a long steaming. Nevertheless: the loss of dyestufi-wherever it occurred-was put up with;

when considering the great acceleration of: the working method resulting by applying these new processes and the'economy'resulting, therefrom;

It has now been found that the formation of the chromium mordant 'd'y'estuff lake, 1'. e. the fixation of the dyestufi on the printed fabrics can considerably be accelerated by using printing pastes containing. beside the: dyestuff, thethick ener' and possibly other usualwadditions suchras formic acid", acetic acid and the like; atcarboxyli'c' 14 Claims. (01-. s -vz'i' 21 acid amide, analkalfchroniate. or bichr'oifiatie as mordant agent, furthermore a solubl'esalt. of an acid deriving froman oxygen" compound'o'f sulphurand possessing reducing'properties; a substance capable of" splitting, ofi a strong acid in the" heat, as well as, i'f"c:onven'ient', anaromatie' compound, such as a polyhydroxy compound orpoly ketone-respectively, which" is capable of performing the reversible reaction quin'one hydro-- quinone' and which m'ay 'bepresent in the form of q-uinone as well as in the form of hydro'quinone and finally containing w:w-dihydroxydiethylsul phidejbyprinting such printing pastes" on the fabrics and forming thechromium lake, without any steaming, b'y'a simple dryingjand' if desired" hanging:

If for instance a fabric consisting. of cellulose fibres is printed: with such a printing paste, dried and left hangin or lying for 48 hours" at 'room' temperature; thenrin'sed and, asu'sua'l for chrom'ium riiordant" dyestuffs; subsequently soa'pe'd',

rinse'd again and dried, there are obtained well fixed'c'hromium mordant" dyestuif prints, without necessitating asteaming operationfor the forma-" tion of the chromium'lake.

, allltho'sei cases; where steaming is impossible; such as, for. instance, for printing. paper, paper hang-- ings, Woven paper and similar "fabricsg 'In this case, the printed paper is dried ona dryin 'cylinder and left lying, whereby thecolours are them selvesnormally fixedi The prints thus obtained are" fast towashing and rubbing.-

It is understoodt-liat chromium inordant "dye' stuff printing pastes obtained according to the above disclosures may also befixed by steaming.

-In this case, a very short steaming of 2 minutes will be sufllcient, this being a lapse of time which heretofore would not. have been sufiicient: for fixation Wheni steaming; is applied, the above mentioned aromatic 'polyhydroxy compounds-orarematib polylretm'esr'respectlvel$ awaitedv aai in .l v 3 most of the cases, also the w:w'-dihydroxydiethylsulphide may be dispensed with in the printing pastes. Also this variation of the process involves a considerable technical improvement compared with the methods known up to now, inasmuch as 5 possessing reducing properties may be enumerated: hydrosulphites, sulphites, thiosulphates,

whereby according to the dyestufi used the most suitable one of the salts will advantageously be selected. I

As acid yielding substances .{Suitable for the process there may be used the salts of a volatile inorganic or organic base with a; strong inorganic or organic acid, the latter being not allowedto disturb the formation of the dyestui'f chromium lake. As examples may be mentioned: ammonium sulphocyanate, ammonium chloride, ammonium sulphate, ammonium nitrate, etc.

As aromatic polyhydroxy compounds which are converted into quinones by oxidation, use maybe made of for instance: hydroquinone, pyrocatechine, resorcinol, pyrogallol, phloroglucine, hydroxyhydroquinone. Suitable aromatic polyketones which are transformed into a hydroquinone by reduction are: a-naphthoquinone, anthraquinone, quinizarine and the like, as well as the sulphonic acids of the substances of both these groups.

All the above mentioned additional products may be added to the printing paste or the latter may be prepared in two separate portions, one portion containing the dyestufl, the accelerator, w:w-dihydroxydiethylsulphide, the thickener and the. acid yielding substance, moreover the salt of an acid derivingjfrom an'oxygen compound of sulphur and possessing reducing properties, the

other one containing the chromium mordant, the aromatic compound, i. e. the polyhydroxy compound or. the polyketone and also the thickener. The two portions will subsequently be mixed up together before printing.

The new process is illustrated'by the following examples; without being limited thereto. The parts are by weight. 7

Example 1 The following printing colour is printed on cotton or staple fibres:

. Parts Chromocitronine R (colour index No. 441) Urea ,3- :w-dihydroxydiethylsulphide 3 Hot water 24.9 Tragacanththickening 50 Ammonium sulphocyanate, solution 1:1 3 Sodium chromate, solution 1:2 6; Sodium thiosulphatasolution 1:1 6 Ammonia 1 Hydroquinone 0.1

The printed material is dried, left lying or hangingat room temperature for 48 hours, then rinsed,

soaped at 60 C., rinsed and dried. 1

":Thus .deep and evenyellow printsyare obtained 4 which are as strong as the prints obtained with chromium acetate by a steaming for 1 hour.

Example 2 The following printing paste is printed on cotton:

' I Parts Dyestuff obtained according to Example 1 of British Patent No. 255,086 3 Urea 3 w:w-dihydroxydiethylsulphide 3 Hot water 24.8 Tragacanth thickening 50 Ammonium sulphocyanate, solution 1:1 3 Sodium chromate, solution 1:2 6 Sodium thiosulphate, solution 1:1 6 Ammonia 1 a-naphthoquinone 0.2

The printed material is dried and steamed for 2 minutes, then rinsed and soaped at 60 C., rinsed and dried.

Thus deep, vivid, orange prints are obtained, which are as deep and vivid as the prints obtained with chromium acetate and by a steaming for 1 hour.

Example 3 The following printing colour printed on cotton or viscose-rayon:

v Parts Dyestuif prepared accordin to Example 1 of the French Patent No. 457,840 3 Urea 3 w:w-dihydroxydiethylsulphide 5 Hot water 22.1 Tragacanth thickening 50 Ammoniumsulphate, solution 1:2 4 Ammonium chromate, solution 122 5.5 Sodium thiosulphate, solution 1:1 6 Ammonia 1 Anthraquinone, 0.4

The printed material is dried and steamed for 2 minutes, then rinsed, soaped at 60 C., rinsed and dried. Thus'deep, even, vivid, yellowish-red prints are obtained, which arerather stronger than prints obtained with chromium acetate by a steaming of 60 minutes.

Example 4 The following printing colour is printed on cotton:

The printed material is dried, left lying for 48 hours, rinsed, soaped at 60 0., rinsed and dried. Thus a deep, even, green print is obtained.

ease-4:71.

Portion A and Portion B are mixed before use. With the paste thus obtained cotton'orviscoserayon is printed. The printed material is dried, allowed to lie for 48 hours,"rinsed;-.soaped at 60 0., rinsed and dried. There:are obtained deep, even,- red prints.

Example6 The following printing colour is printed "on cotton:

, Parts Chromocitronine 3 R (colour index No. 441); 3 Urea '3 w:w-dihydroxydiethylsulphide 3 Hot Water 1' I $23.9 Tragacanth thickening 50 Ammonium sulphatefsolution 1:2 14 Sodium ohromate, solution 1:2 6 Ammonium sulphite, solution 1:1 6 Ammonia 1 Hydroquinone 0.1

The printed material is zdried,r-le ft lying .for' 48 hours, rinsed, soaped at 60 ;,rinsed and'driedr Thus deep yellow prints are obtained..

Example 7 The following printing paste is'prepared Parts Chromocitronine R (colour index No5441); i '3 Acetamide; l 3

w:w dihydroxydiethylsulphide on- '5- Water 229 Tragacanth thickening a The printedmaterial -is dried, .left lying-010,4 8 hours,. rinsed, soapedat 60C., rinsed and dried. Thus deep, even, yellow prints are obtained.

The quantity of resorcinol used in this example may Jaereplaoed by 0.2 part of pyrogallic sulphonic acid, the results being not modified inany Way. 1 v 1 6y v Exempla 8" The following printing aste-is prepared:

Parts Blue .1900 double (colour index No. 892).. 3 Formie'a'cid 1 2 Urea'" 3 w w -dihydroxydiethyls'ulphide I; .1- 1 3 Hot water: Traga'caritn'thickening;;';: 50

Dissolve, cool downand addz' Sodium hydrosulphite-powder=' i 4 Ammonium nitrate crystne1.1116. 4

Sodium chromate, solution 1:2 1.5 Formic acid 85% 2 The printed cellulose material is dried and left lying forAa-hours,rinsed;lsoapedat 60 0., rinsed and'dried Thus' vividfideep; -reddishblue pr'intsare ob tained, which are as deep as the blue prints obtained with the same quan tity of dyestufi and with-chromium acetate by a steaming or 60 minutes.

Example 9 The "following printing colour "is printed H on viscose rayon, staple fibre or cotton:

. Parts Dyestufi obtained according to Example--2 of the British Patent No. 3796/1914 3 Urea 3 Hot water 1 28 Tragacanth thickening 50 Ammonium sulphocyanate, 'solution -.1:=1 3 Sodium chromate, solution 1:2 6 Sodium thiosulphate, solution 1:1 6 Ammonia 1 The printed material is dried, steamed for. 2 minu'tesin the Mather-Platt-agerpwashed, soaped at '60- 6; and finished;

Thus th'ere are obtained vivid; deep pink prints,

which are at least --asstrong as the pink prints obtainable with the samequantity of dyestuff and with chromium acetate by a steaming for 1 hour.

Example 10 The following printingzpaste is eprinted on cotton, viscose rayon or staple fibre:

Parts Chromorhodine'BB colour index No. 762) 3 Urea 3 Hot water 27.5 Tragacanth thickening. 50 Ammonium sulphate, solution--1:'-2 4 Ammonium chromate, solution 1 :'2 5.5 Sodium thiosulphate; solution 1:"1 6 Am moniare 1 A The printed materialis dried; steamed for 2 minutes'rinsed, soaped at 60 C., rinsed and dried.

Thus there are obtained vivid, deep pink prints which are at least as strong as the prints obtamed-with the same quantity of dyestuii and with --chromium-acetate by asteamingfor 60 minutes.

Example 11 The following printing colour is printed on cotton:

The printed material is dried, left lying for 48 hours, rinsed, soaped at 50 (3., rinsed again and finished. 1

Thus vivid, deep, orange prints are obtained, which are as strong as the prints obtained with chromium acetate by a steaming duration of 1 hour.

Example 12 The following printing colour is printed on cotton:

The printed material is dried, left lying for 48 hours, rinsed, soaped at 50 0., rinsed again and finished.

Thus deep, vivid green prints are obtained, which are as strong as the green prints obtained with the same quantity of dyestuff and with chromium acetate by a steaming for 60 minutes.

Example 13 The following printing paste is printed on cotton:

Parts Chrome violet CB double (colour index No.

727) 3 Urea 3 w:w-dihydroxydiethylsulphide 5 Hot water 22.1 Tragacanth thickening 50 Ammonium sulphate, solution 1 :2 4 Ammonium chromat'e, solution 1:2 5.5 Ammonia 1 Sodium thiosulphate, solution 1:1 6 Anthraquinone 0.4

The printed material is dried, left lying for 48 hours or steamed during 2 minutes, rinsed, soaped at 50 0., rinsed again and finished.

Thus there are obtained deep, vivid, violet prints, which are at least as strong as the violet prints obtained with the same quantity of dyestuff and with chromium acetate by a steaming for 60 minutes.

8 Example 14 Parts Dyestuif obtained according to the example of the French Patent No. 398,980 3 Urea 3 w:w-dihydroxydiethylsulphide 5 Water '1 25.8 Tragacanth thickening 50 Ammonium sulphate, solution 1:2 4 Ammonium chromate cryst 1.8 Sodium thiosulphate, solution 1: 1 6 Ammonia 1 Anthraquinone powder 0.4

The printed material is dried, left lying for 48 hours, rinsed, soaped at 50 C., rinsed again and dried. 1

Thus there are obtained deep, even orange prints corresponding in every respect to the orange prints obtainable with chromium acetate by a steaming for 60 minutes.

Examples 17 The following printing pastes are printed on wall-paper:

. Dyestufi obtained according to Example 2 of the British Patent No. 3,796/14 Dyestufi obtained according to Example 1 of the British Patent No. 500,075

Dyestufi obtained according to Example 1 of the British Patent No. 255,086

Chrcmocitronine R (Colour Index No. 441) Urea m Q dihydroxydicthylsulphide Water 1 Tragacanth thickening Ammonium sul hate, solu- :tion 1 :2 4

Ammonium chromate cryst Sodium thiosulphate, solution 1:1 6

Anthraquinone powder Ammonia The printed wall paper is dried on drying drums and hung up for 48 hours.

Thus deep, bright and well fixed prints are obtained, which according to Example 15 are pink, and according to Example 16 green, while according to Example 17 they are brownish orange and according to Example 18 yellow.

All the prints are fast to rubbing and the printed paper-hangings may be washed without damage.

What I claim is:

1. A process for printing cellulosic material with chrome dyestuifs, which comprises printing onto the said cellulosic material a printing paste containing, besides the dyestufi, a thickener, a

water-soluble carboxylic acid amide, as chromium mordant an alkali metal chromate, a substance which splits off a strong acid in the heat and, as characteristic additions, a water-soluble salt of an inorganic acid derived from an oxygen compound of sulphur and possessing reducing properties, an aromatic compound capable of performing the reversible reaction quinone hydroquinone, and w:w'-dihydroxydiethyl sulphide, and subjecting the obtained prints to a drying operation.

2. A process for printin cellulosic material with chrome mordant dyestuffs, which comprises printing onto the said cellulosic material a printing paste containing, besides the dyestuff, a

thickener, a water 'soluble carboxylic acid amide,

.a's chromium mordantan.-:-alkali metal chromate,

a substance which splits off a- 'strong acid1in the heat and, as characteristic additions, a Watersoluble salt of an inorganic acid derived from an oxygen compound of sulphur and possessing re ducing properties, an aromatic compound capable of performing the reversible reaction quinone hydroquinone, and w:w"'-dihydroxydiethyl sulphide, and subjecting the obtained prints to a drying operation and StGamiHg ffOr 2 minutes.

3. A process for printing cellulosic material with chrome mordant dyestuffs, which comprises printing onto-the saidcellul-os'ic in-ateria-la printing paste containing, besides the dyestufi, a

thickener, urea, as chromium mordant an alkali metal chromate, a substance which splits off a strong acid in the heat and, as characteristic additions, a water-soluble salt of an inorganic acid derived from an oxygen compound of sulphur and possessing reducing properties, an aromatic compound capable of performing the reversible reaction quinone hydroquinone, and mid-dihydroxydiethyl sulphide, and suspending the printed cellulosic material until dry.

4. A process for printing cellulosic material with chrome mordant dyestufis, which comprises printing onto the said cellulosic material a printing paste containing, besides the dyestuff, a thickener, a Water-soluble carboxylic acid amide, as chromium mordant sodium chromate, a substance Which splits olT a strong acid in the heat and, as characteristic additions, a water-soluble salt of an inorganic acid derived from an oxygen compound of sulphur and possessing reducing properties, an aromatic compound capable of performing the reversible reaction quinone hydroquinone, and w:w-dihydroxydiethyl sulphide, and suspending the printed cellulosic ma terial until dry.

5'. A process for printing cellulosic material with chrome mordant dyestuffs, which comprises printing onto the said cellulosic material a printing paste containing, besides the dyestuff, a thickener, a Water-soluble carboxylic acid amide, as chromium mordant an alkali metal chromate, ammonium sulphate and, as characteristic additions, a water-soluble salt of an inorganic acid derived from an oxygen compound of sulphur and possessing reducing properties, an aromatic compound capable of performing the reversible reaction quinone hydroquinone, and wIw'-dlhydroxydiethyl sulphide, and suspending the printed cellulosic material until dry.

6. A process for printing cellulosic material with chrome mordant dyestuffs, which comprises printing onto the said cellulosic material a printing paste containing, besides the dyestuff, a thickener, a water-soluble carboxylic acid amide, as chromium mordant an alkali metal chromate, a substance which splits off a strong acid in the heat and, as characteristic additions, sodium thiosulphate, an aromatic compound capable of performing the reversible reaction quinone hydroquinone, and w w'-dihydroxydiethyl sulphide, and suspending the printed cellulose material until dry.

7. A process for printing cellulosic material with chrome mordant dyestuffs, which comprises printing onto the said cellulosic material a printing paste containing, besides the dyestuff, a thickener, a water-soluble carboxylic acid amide, as chromium mordant an alkali metal chromate, a substance which splits ofi a strong acid in the heat and, as characteristic additions, a water- "amide; as

soluble salt era-n inorganic acid derived' from an oxygen '"compound' of-- sulphur and possessing reducing properties, anthraquinoneand em -dihydroxydiethyl sulphide, and suspending the printed material until dry;

BJ'A -proce'ss for printing cellulose material with chrome mordant dyestuffs, which comprises printing onto the said-cellulosic material a printing paste "containing besides the dyestufi, a thickener,- I *a' water-soluble car'boxylic acid hromium mordant an alkali metal chromate, -a" s ubs'tance which splits off a strong acid in the heat and, as characteristic additions, a water-soluble salt of an inorganic acid-derived from an oxygerr compcund of sulphur and possessing reducing properties, hydroquinone and w:w-dihydroxydiethyl sulphide, and suspending the printed cellulosic material until dry.

9. A process for printing cotton with chrome mordent dyestufis, which comprises printing onto the cotton a printing paste containing, besides the dyestufi, a thickener, a water-soluble carboxylic acide amide, as chromium mordant an alkali metal chromate, a substance which splits off a strong acid in the heat and, as characteristic additions, a Water-soluble salt of an inorganic acid derived from an oxygen compound of sulphur and possessing reducing properties, an aromatic compound capable of performing the reversible reaction quinone hydroquinone and w w'-dihydroxydiethyl sulphide, and suspending the printed cotton until dry.

10. A process for printing paper-hangings with chrome mordant dyestufis, which comprises printing onto the paper-hangings a printing paste containing, besides the dyestufi, a thickener, a water-soluble carboxylic acid amide, as chromium mordant an alkali metal chromate, a substance which splits off a strong acid in the heat and, as characteristic additions, a watersoluble salt of an inorganic acid derived from an oxygen compound of sulphur and possessing reducing properties, an aromatic compound'capable of performing the reversible reaction quinone hydroquinone, and w w-dihydroxydiethyl sulphide, and subjecting the obtained prints to a drying operation and hanging the same.

11. A printing paste containing beside a chrome mordant a dyestuff, a thickener, a watersoluble carboxylic acid amide, as chromium mordant, an alkali metal chromate, a substance which splits off a strong acid in the heat and, as characteristic additions, a water-soluble salt of an inorganic acid derived from an oxygen compound of sulphur and possessing reducing properties, an aromatic compound capable of performing the reversible reaction quinone hydroquinone, and w w'-dihydroxydiethyl sulphide.

12. A printing paste containing beside a chrome mordant dyestufi, a thickener, a watersoluble carboxylic acid amide, as chromium mor-- dant, an alkali metal chromate, a substance which splits off a strong acid in the heat and, as characteristic additions, sodium thiosulphate, an aromatic compound capable of performing the reversible reaction quinone hydroquinone, and w w'-dihydroxydiethyl sulphide.

13. A printing paste containing beside a chrome mordant dyestuff, a thickener, a watersoluble carboxylic acid amide, as chromium mordant. an alkali metal chromate, a substance which splits off a strong acid in the heat and, as characteristic additions, a water-soluble salt of an inorganic-acid. derived frorn pxygen compound, of sulphur and: possessing, reducing properties, anthraquinone, and; q: w-dihydroxyethyl su1phide.-

14. A printing paste 'corrtaiuing "beside" a 5 chrpme-m0rdant dyestufif, a thickener, a watersoluble carboxylic acidamide, as chromium mordant, an alkali metal chromate, a substance which splits off a strong acid in the heat and, as

characteristic additions, a water-soluble salt cf 10 an inorganic acid derived from an oxygen compound of sulphur and possessing reducing properties, hydroquinone, and w'-dihydroxyd1- ethyl sulphide,

ERNST 'TSCHANQ 15 12 REFERENCES CITED v The following references are of record in the file of this patent:

UNITEI STATES PATENTS Germany Oct. 15, 1908 

